CN109852145A - Biology base electrically conductive ink and its preparation method and application - Google Patents
Biology base electrically conductive ink and its preparation method and application Download PDFInfo
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- CN109852145A CN109852145A CN201811618102.4A CN201811618102A CN109852145A CN 109852145 A CN109852145 A CN 109852145A CN 201811618102 A CN201811618102 A CN 201811618102A CN 109852145 A CN109852145 A CN 109852145A
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Abstract
The present invention relates to a kind of biology base electrically conductive inks and its preparation method and application, and the electrically conductive ink contains protein-modified carbon nanotube, nano silver, carbon black and water-base resin, and the auxiliary agent being added as needed.The present invention adds the filler material of nano silver and carbon black as conducting pigment in carbon nanotube ink, can significantly promote the electric conductivity of ink, have wide range of applications；In addition, electrically conductive ink of the invention is biological based water-based ink, and using water-base resin as binder, safety and environmental protection.
Description
Technical field
The invention belongs to package printing material technical fields, and in particular to a kind of degradable nano grade of biology base is aqueous to be led
Electric ink and preparation method.
Background technique
Printing effect, efficiency and mechanism of traditional ink etc. were already mature, and printed matter is also given in the innovation of printing technology
More beautiful, fuller, more colorful presentation are brought, to meet the needs of consumer is to Diversification of products.On the other hand, large
Except the diversification printing of commodity, personal printing and functional printing become the object that consumer competitively chases, and also become
Effective publicity measures of manufacturer.Personal printing and functional printing technology need to print ink and not only have common ink
Color present, the functions such as information transmitting, with greater need for having property, such as safety, degradability, electric conductivity, magnetism, anti-
Electrostatic, warm denaturation, easy sprayability, fluorescence etc., wherein especially using the safety and environmental protection of ink and electric conductivity as the most important thing.It is first
First, safety and environmental protection are the focus places of the industries such as every profession and trade especially coating, ink, while being also the focus of consumer.
With the raising of the level of consumption, consumer to the packages printing of product it is beautiful and in terms of propose higher need
It asks, the demand of ink is also being continuously increased, but the solvent-based ink of good quality is strong to the pollution of environment and to human body
Health has tremendous influence, and therefore, the safety and ecological requirements of ink are the key points of its sustainable development.
Conductive sexual function ink becomes the material of current ink area most development potentiality and commercial value, because it makes to print
Brush technology has surmounted the scope of printing image carrier on the transmitting ink to stock of script, develops to the intelligence system of mechanical industry
Make with minute manufacturing, the transistor of electronics and information industry and photoelectric information transmitting and Art Design field functionalized design and
The fields such as interactive experience make the science and technology based on traditional printing technology climb up natural science again with the posture of epoch seaman
Stage.Electrically conductive ink is really a kind of special conductive coating, it and bionics plastics, waste be converted into energy pyroelectric technology,
The new materials such as carbon fiber are cited as changing one of following manufacturing nine kinds of materials together, and electrically conductive ink is in printed electronic material
Field plays a significant role, in sensor, radio electronic label (RFID), circuit board, 3D printing, display screen (LED and OLED)
There is important application with fields such as batteries.The high conductivity of printed electronic material, organise, lightweight and safety and environmental protection demand are
The direction of its future development is that printed electronic market is flourished especially in terms of the breakthrough of new technology and the reduction of cost
Basis.It is worth noting that, with the rise of electrically conductive ink, production and application range will further expansion, this also will
It is related to the safety and environmental protection problem of ink and printing industry.How to make functional ink more environmentally protective, using which kind of printing
Technology is the carrier of environment-protection functional ink, how to further increase the electric conductivity etc. of electrically conductive ink, and these problems are all printings
Industry, the key problem of especially emerging printed electronic industry concern.
Summary of the invention
Technical problem present in currently available technology is, in current electrically conductive ink, carbon black and nano silver are as conductive
The application range of ink main pigments is relatively narrow, using carbon black as the poor (resistance range 10 of the electrically conductive ink electric conductivity of filler4-106
Ω), and carbon black disperses unevenly, to be easy precipitating deposition occur in ink bottom in ink；The precious metals such as nano silver exist
It is not easy to disperse in polymer binder resin (such as epoxy resin, polyurethane, polyacrylate), and metal packing is mutual
Between there are strong collision and inducing action (Depletion-induced Interaction), be easy to appear agglomeration
And precipitate, reduce the operability and printing of composite material.Therefore dispersibility, electric conductivity and the safety of electrically conductive ink
Need to be further increased.
The present inventor once used lysozyme and carbon nanotube as the raw material of biology base conducting pigment, assisted with aqueous poly- ammonia
Ester lotion and related water-soluble additive prepare environment protection biological base water-soluble conducting ink, but current apparently the present inventor was once
Carbon nanotube is only used only as conducting pigment in the technical solution of research, and electric conductivity is weaker, is suitable for semiconductor material.
The present inventor is in order to solve the above technical problems, the present inventor creatively adds nano silver and carbon black as conductive face
The filler material of material, nano silver and carbon black are micro-nano granules, can be filled in the carbon nano tube network of winding, enhancing
Conductive network, to significantly promote its electric conductivity.In addition, the present inventor also provides a kind of simple process, environmental-friendly life
The preparation method of object base electrically conductive ink.
Specifically, the invention proposes following technical solutions:
On the one hand, the present invention provides a kind of biology base electrically conductive ink, the electrically conductive ink contains protein-modified carbon and receives
Mitron, nano silver, carbon black and water-base resin, and the auxiliary agent being added as needed.
Preferably, above-mentioned electrically conductive ink contains protein-modified carbon nanotube 5-20 parts by weight, nano silver, carbon black and water
Property resin 14-55 parts by weight, and the auxiliary agent being added as needed.
Preferably, above-mentioned electrically conductive ink contains protein-modified carbon nanotube 5-20 parts, nano silver in parts by weight
0.0002-0.001 parts, 5-10 parts of carbon black, 14-55 parts of water-base resin, and be added as needed 2-8 parts of auxiliary agent；Preferably
It is that the electrically conductive ink contains 20-80 parts of water in parts by weight；
It may further be preferable that the electrically conductive ink contains protein-modified carbon nanotube 8-12 parts, water in parts by weight
25-35 parts, 0.0003-0.0008 parts of nano silver, 6-9 parts of carbon black, 20-30 parts of water-base resin, and what is be added as needed are helped
4-8 parts of agent；
It may further be preferable that the electrically conductive ink contains protein-modified carbon nanotube 9-11 parts, water in parts by weight
28-32 parts, 0.0005-0.0008 parts of nano silver, 6-9 parts of carbon black, 22-27 parts of water-base resin, and what is be added as needed are helped
5-8 parts of agent.
Preferably, above-mentioned electrically conductive ink, wherein the protein is selected from zymoprotein, preferably lysozyme.
Preferably, above-mentioned electrically conductive ink, wherein the activity of the lysozyme is 30000-70000；Preferably
40000-60000。
Preferably, above-mentioned electrically conductive ink, wherein the carbon nanotube is selected from single-walled carbon nanotube and/or multi wall carbon
Nanotube；Preferably, the carbon nanotube diameter is 1-100nm, preferably 20-50nm.
Preferably, above-mentioned electrically conductive ink, wherein the particle size range of the nano silver is 2-90nm, preferably 12-
15nm。
Preferably, above-mentioned electrically conductive ink, wherein the carbon black purity is higher than 90%.
Preferably, above-mentioned electrically conductive ink, wherein the water-base resin be selected from aqueous polyurethane, aqueous epoxy resins,
Water-based acrylic resin.
Preferably, above-mentioned electrically conductive ink, wherein the auxiliary agent is selected from levelling agent and/or defoaming agent, it is preferred that
The levelling agent is selected from paraffin, acrylic acid levelling agent, ethylene oxide, propylene oxide and/or organosiloxane class levelling agent, preferably
Paraffin；The defoaming agent is selected from polysiloxanes, polyethers defoaming agent, preferably polysiloxanes；It may further be preferable that the conduction
Ink contains 1-4 parts of levelling agents, 1-4 parts of defoaming agents in parts by weight.
Preferably, above-mentioned electrically conductive ink, wherein the protein-modified carbon nanotube is by receiving protein and carbon
Separation supernatant is made after mitron mixing.
Preferably, above-mentioned electrically conductive ink, wherein the protein and the mass ratio of carbon nanotube are 1:0.8-3.
On the other hand, the present invention also provides the preparation methods of above-mentioned electrically conductive ink, comprising the following steps:
Step (1): protein-modified carbon nanotube, Nano silver solution and carbon black are mixed to get composite conducting pigment；
Step (2): the composite conducting pigment is mixed with water-base resin and the auxiliary agent being added as needed, is obtained aqueous
Composite material；With
Step (3) sieves the aqueous composite material by sieve, and the mixture under sieve is taken to obtain electrically conductive ink；It is preferred that
, the sieve is 100-200 mesh.
Preferably, above-mentioned preparation method, wherein by weight, protein-modified carbon nanotube is 5-20 parts, nanometer
Silver-colored solution is 2-8 parts, carbon black is 5-10 parts, water-base resin is 14-55 parts.
Preferably, above-mentioned preparation method, wherein in step (1), the mixing includes dispersion step, it is preferred that
The dispersion passes through ultrasonic disperse, it is further preferred that, the ultrasonic disperse power is 200-500W, preferably 260-
400W；It may further be preferable that the dispersion is dispersed by cell pulverization instrument.
The present invention also provides electrically conductive inks in the above way obtained.
On the other hand, the present invention provides a kind of composite conductive layers, electrically conductive inks and substrate of the invention.
Preferably, above-mentioned composite conductive layers, the substrate are selected from resin, silicon wafer and/or glass.
On the other hand, the present invention also provides above-mentioned electrically conductive ink print field application, preferably in printed electronic
The application of Material Field, further preferably in sensor, radio electronic label, circuit board, 3D printing, display screen and field of batteries
Application.
The beneficial effect comprise that
1, electrically conductive ink of the invention is biological based water-based ink, using water-base resin as binder, safety and environmental protection.The present invention
In preferred scheme, take water as a solvent, more safety and environmental protection.
2, biology base water-soluble conducting ink electric conductivity of the invention is good, has wide range of applications.
With reference to the accompanying drawing with each specific embodiment, the present invention and its advantageous effects are described in detail:
Detailed description of the invention
Fig. 1-a: lysozyme modified carbon nano-tube scanning electron microscope (SEM) photograph, amplification factor 1K.
Fig. 1-b: lysozyme modified carbon nano-tube scanning electron microscope (SEM) photograph, amplification factor 20K.
Fig. 2: composite conducting pigment conductive path figure prepared by embodiment 1.
Fig. 3: the square resistance of electrically conductive ink prepared by embodiment 1 on different substrate materials.
Fig. 4: the square resistance of electrically conductive ink prepared by embodiment 2 on different substrate materials.
Fig. 5: the square resistance of electrically conductive ink prepared by embodiment 3 on different substrate materials.
Fig. 6: the square resistance of electrically conductive ink prepared by embodiment 4 on different substrate materials.
Fig. 7: the square resistance of electrically conductive ink prepared by embodiment 5 on different substrate materials.
Specific embodiment
The present invention is described in detail With reference to embodiment.Following implementation will be helpful to this field
Technical staff further understands the present invention, but the invention is not limited in any way.It should be pointed out that the common of this field
For technical staff, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to this
The protection scope of invention.
As described above, the purpose of invention is the electric conductivity for solving the problems, such as how to improve electrically conductive ink and safety.
In order to solve the above-mentioned technical problem, the present invention mixes carbon nanotube and antalzyme protein matter, in the effect of ultrasound
Under prepare the composite conducting pigment of favorable dispersibility, then by itself and water-base resin, environment-friend auxiliaries, Nano silver solution and carbon black
Deng mixing, the good biology base electrically conductive ink of electric conductivity is prepared by being uniformly dispersed.
Carbon nanotube (CNTs) and antalzyme protein matter are mixed with protein-modified carbon nanotube, made using lysozyme
For dispersing agent, to improve dispersibility and stability of the CNTs in system of the water as continuous phase, it is good to prepare electric conductivity
CNTs dispersion liquid.The principle of lysozyme modified carbon nano-tube are as follows: there are many active groups on lysozyme surface, can be with CNTs
Surface forms more binding site, and there are stronger Van der Waals fors with the surface CNTs.Moreover, the orderly peptide chain of lysozyme
Structure also makes the intermolecular force on itself and the surface CNTs that ordering be presented, to make CNTs that can stablize in lysozyme soln
Dispersion, form stable dispersion liquid.
A kind of currently preferred biology base nano conductive printing ink, contains protein-modified carbon nanotube, nano silver, carbon black
And water-base resin, and the auxiliary agent being added as needed.The preferred lysozyme of protein, the folding knot of lysozyme macromolecular chain
Structure can form special pouch-type space structure, can effectively be connected with carbon nanotube.The carbon nanotube can be selected from single wall carbon
Nanotube and multi-walled carbon nanotube.As long as the water-base resin can be with water-based ink resin, such as polyurethane, epoxy
Resin, acrylic resin etc..
Currently preferred a kind of biology base nano conductive printing ink, by following raw materials and proportion (according to parts by weight) preparation
Form: lysozyme (activity 40000) 5-20 parts, 5-20 parts of multi-walled carbon nanotube, 2-8 parts of Nano silver solution, is gone by 2-10 parts of carbon black
20-80 parts of ionized water, 14-55 parts of aqueous polyurethane, 1-4 parts of liquid paraffin, 1-4 parts of polysiloxanes.It is currently preferred above-mentioned
Weight can both form intact conductive network, avoid conductive filler very few and there is a problem of conductive open circuit, and have
There is excellent printing performance, avoids conductive filler from crossing and often have the insufficient problem of bonding.
A kind of preparation method of currently preferred biology base nano conductive printing ink, specific steps are as follows:
(1) the lysozyme powder that activity is 40000 is weighed, is dissolved using deionized water, is configured to 10-3M concentration
Colorless and transparent Lysozyme in Aqueous Solution；
(2) quantitatively untreated multi-walled carbon nanotube (MWCNTs) is weighed, is poured slowly into Lysozyme in Aqueous Solution,
It is placed on ultrasonic vibration 5 minutes in supersonic wave cleaning machine；
(3) mixed liquor in (2) is placed under ice bath environment, using ultrasonic cell disrupte instrument (the new sesame biotechnology in Ningbo
Limited liability company, model: JY92-IIN) ultrasound is carried out to it 1 hour, divide MWCNTs sufficiently in Lysozyme in Aqueous Solution
It dissipates, obtains uniformly mixed black mixed liquor.Then it is placed in centrifuge (Hunan instrument CTK132R type) at 6000 revs/min
Under conditions of clock, after centrifugation 15 minutes, supernatant is taken, MWCNTs/ lysozyme composite dispersion liquid is obtained.
(4) the MWCNTs/ lysozyme composite dispersion liquid and Nano silver solution that will be obtained, carbon black mixing, in magnetic stirrer
On, 200rmp revolving speed is stirred 3h under the conditions of 40 DEG C, then complex liquid is dispersed to 3 minutes (cell powders in cell pulverization instrument
Broken instrument power regulation is 200-500W, preferably 260-400W)；Finally dispersion liquid is placed in 50 DEG C of thermostatic drying chamber and is done
Dry 12 hours, obtain biology base composite conducting pigment.
(5) product in (4) is mixed with auxiliary agents such as aqueous polyurethane, liquid paraffin and polysiloxanes and pours into ball mill (south
Capital instrument plant, university QM-3SP planetary ball mill) after mixing, high speed grinding is carried out to it using agate ball, revolving speed is 600 revs/min
Clock, time are 1 hour, obtain uniformly mixed aqueous composite material；
(6) mixture is sieved by 200 mesh screens, takes the mixture under sieve, continued ultrasonic disperse 5 minutes, then will
Mixture is coated on clean substrate, then will be applied cloth base material and be placed in drying 24 hours in 60 DEG C of drying boxes, and composite guide is obtained
Electric layer.By low temperature drying, traditional high temperature, short time sintering step is substituted, makes the dry connection of conductive layer, is formed continuous conductive
Layer.
Illustrate electrically conductive ink of the invention below by specific embodiment, and electrically conductive ink performance is detected.
Used each reagent and instrument source are as follows in following example, and the instrument and reagent that do not record are that this field is general
The instrument or reagent that logical technical staff can routinely determine:
1 embodiment agents useful for same of table and instrument
The present inventor uses lysozyme modified carbon nano-tube, and by scanning electron microscopic observation carbon nanotube state, with confirmation
For lysozyme in conjunction with carbon nanotube, the step of lysozyme modified carbon nano-tube, is as follows:
(1) the lysozyme powder that the activity of 10 parts by weight is 40000 is weighed, is dissolved, is configured to using deionized water
10-3The colorless and transparent Lysozyme in Aqueous Solution of mol/L concentration；
(2) the untreated carbon nanotube of 10 parts by weight (CNTs) is weighed, is poured slowly into Lysozyme in Aqueous Solution, is put
Set ultrasonic vibration 5 minutes in supersonic wave cleaning machine.
(3) mixed liquor in (2) is placed under ice bath environment, using ultrasonic cell disrupte instrument (the new sesame biotechnology in Ningbo
Limited liability company, model: JY92-IIN) ultrasound is carried out to it 1 hour, keep CNTs fully dispersed in Lysozyme in Aqueous Solution,
Obtain uniformly mixed black mixed liquor.Then it is placed in centrifuge under conditions of 6000 revs/min, is centrifuged 15 points
Zhong Hou takes supernatant, obtains CNTs/ lysozyme composite dispersion liquid.
CNTs/ lysozyme composite dispersion liquid sample is dropped evenly on silicon wafer, uses SEM to observe its microcosmic shape after dry
Looks, as shown in Fig. 1-a and 1-b.Under low power mode, as shown in Fig. 1-a, the coating of CNTs/ lysozyme desciccator diaphragm is comparatively dense, says
Bright CNTs is uniformly dispersed in lysozyme.Under high power mode, as shown in Fig. 1-b, it may be observed that disordered state is presented in CNTs, but
To be completely embedded between each other, it is theoretical by percolation conduction it is found that unordered CNTs under dry bacteriolyze enzyme effect mutually it
Between form fine and close access, by the peptizaiton of lysozyme between each nanotube, be evenly distributed in dispersion liquid, mutually it
Between there are certain molecular separating force, after then lysozyme soln is dry, nanotube forms entanglement between each other, rather than script is received
Loose condition (of surface) existing for mitron powder mutually forms bridge joint between the nanotube after entanglement, can be confirmed that lysozyme has succeeded
It is connected in carbon nanotube.
Embodiment 1
Biology base nano conductive printing ink is prepared using the raw material of parts by weight in table 2:
2 biology base electrically conductive ink raw material proportioning table (parts by weight) of table
| Lysozyme | Multi-walled carbon nanotube | Aqueous polyurethane | Liquid paraffin | Polysiloxanes | Deionized water | Nano silver solution | Carbon black |
| 10 | 10 | 25 | 2 | 2 | 30 | 3 | 8 |
(1) the lysozyme powder that the activity of 10 parts by weight is 40000 is weighed, is dissolved, is configured to using deionized water
10-3The colorless and transparent Lysozyme in Aqueous Solution of mol/L concentration.
(2) the untreated multi-walled carbon nanotube of 10 parts by weight (MWCNTs) is weighed, it is water-soluble to be poured slowly into lysozyme
In liquid, it is placed on ultrasonic vibration 5 minutes in supersonic wave cleaning machine.
(3) mixed liquor in (2) is placed under ice bath environment, carries out ultrasound to it using ultrasonic cell disrupte instrument 1 hour,
Keep MWCNTs fully dispersed in Lysozyme in Aqueous Solution, obtains uniformly mixed black mixed liquor.Then it is placed on being centrifuged
In machine under conditions of 6000 revs/min, after centrifugation 15 minutes, supernatant is taken, MWCNTs/ lysozyme composite dispersion liquid is obtained.
(4) by obtained MWCNTs/ lysozyme composite dispersion liquid and 3 parts of Nano silver solutions, 8 parts of carbon black mixing, in magnetic force
On blender, 200rmp revolving speed is stirred 3h under the conditions of 40 DEG C, then disperses complex liquid 3 minutes in cell pulverization instrument
(cell pulverization instrument power regulation is 270W)；Dispersion liquid is finally placed in drying 12 hours in 50 DEG C of thermostatic drying chamber, is obtained
To biology base composite conducting pigment.
(5) by the poly- silicon of product and the aqueous polyurethane of 25 parts by weight, the liquid paraffin of 2 parts by weight and 2 parts by weight in (4)
After ball mill mixing is poured into the mixing of the auxiliary agents such as oxygen alkane, high speed grinding is carried out to it using agate ball, revolving speed is 600 revs/min, when
Between be 1 hour, obtain uniformly mixed aqueous composite material.
(6) mixture is sieved by 200 mesh screens, takes the mixture under sieve, continued ultrasonic disperse 5 minutes, then will
Mixture is respectively coated on clean PET, silicon wafer and glass, then is placed in drying 24 hours in 60 DEG C of drying boxes, is answered
Close conductive layer.
It is respectively the composite conducting pigment conductive path figure of the embodiment of the present invention 1 shown in Fig. 2.
The biology base electrically conductive ink that Fig. 3 show the preparation of embodiment 1 applies on different substrate materials (PET, silicon wafer and glass) surface
Square resistance after cloth, square resistance average value are as shown in table 7.
Embodiment 2
Biology base nano conductive printing ink is prepared using the raw material of parts by weight in table 3:
3 biology base electrically conductive ink raw material proportioning table (parts by weight) of table
| Lysozyme | Multi-walled carbon nanotube | Aqueous polyurethane | Liquid paraffin | Polysiloxanes | Deionized water | Nano silver solution | Carbon black |
| 10 | 10 | 25 | 2 | 2 | 30 | 5 | 8 |
(1) the lysozyme powder that the activity of 10 parts by weight is 40000 is weighed, is dissolved, is configured to using deionized water
10-3The colorless and transparent Lysozyme in Aqueous Solution of mol/L concentration.
(2) the untreated multi-walled carbon nanotube of 10 parts by weight (MWCNTs) is weighed, it is water-soluble to be poured slowly into lysozyme
In liquid, it is placed on ultrasonic vibration 5 minutes in supersonic wave cleaning machine.
(3) mixed liquor in (2) is placed under ice bath environment, carries out ultrasound to it using ultrasonic cell disrupte instrument 1 hour,
Keep MWCNTs fully dispersed in Lysozyme in Aqueous Solution, obtains uniformly mixed black mixed liquor.Then it is placed on being centrifuged
In machine under conditions of 6000 revs/min, after centrifugation 15 minutes, supernatant is taken, MWCNTs/ lysozyme composite dispersion liquid is obtained.
(4) by obtained MWCNTs/ lysozyme composite dispersion liquid and 5 parts of Nano silver solutions, 8 parts of carbon black mixing, in magnetic force
On blender, 200rmp revolving speed is stirred 3h under the conditions of 40 DEG C, then disperses complex liquid 3 minutes in cell pulverization instrument
(cell pulverization instrument power regulation is 300W)；Dispersion liquid is finally placed in drying 12 hours in 50 DEG C of thermostatic drying chamber, is obtained
To biology base composite conducting pigment.
(5) by the poly- silicon of product and the aqueous polyurethane of 25 parts by weight, the liquid paraffin of 2 parts by weight and 2 parts by weight in (4)
After ball mill mixing is poured into the mixing of the auxiliary agents such as oxygen alkane, high speed grinding is carried out to it using agate ball, revolving speed is 600 revs/min, when
Between be 1 hour, obtain uniformly mixed aqueous composite material.
(6) mixture is sieved by 200 mesh screens, takes the mixture under sieve, continued ultrasonic disperse 5 minutes, then will
Mixture is respectively coated on clean PET, silicon wafer and glass, then is placed in drying 24 hours in 60 DEG C of drying boxes, is answered
Close conductive layer.
Fig. 4 is after biology base electrically conductive ink prepared by embodiment 2 is coated on different substrate materials (PET, silicon wafer and glass) surface
Square resistance, square resistance average value is as shown in table 7.
Embodiment 3
Biology base nano conductive printing ink is prepared using the raw material of parts by weight in table 4:
4 biology base electrically conductive ink raw material proportioning table (parts by weight) of table
| Lysozyme | Multi-walled carbon nanotube | Aqueous polyurethane | Liquid paraffin | Polysiloxanes | Deionized water | Nano silver solution | Carbon black |
| 10 | 10 | 25 | 2 | 2 | 30 | 8 | 8 |
(1) the lysozyme powder that the activity of 10 parts by weight is 40000 is weighed, is dissolved, is configured to using deionized water
10-3The colorless and transparent Lysozyme in Aqueous Solution of mol/L concentration.
(2) the untreated multi-walled carbon nanotube of 10 parts by weight (MWCNTs) is weighed, it is water-soluble to be poured slowly into lysozyme
In liquid, it is placed on ultrasonic vibration 5 minutes in supersonic wave cleaning machine.
(3) mixed liquor in (2) is placed under ice bath environment, carries out ultrasound to it using ultrasonic cell disrupte instrument 1 hour,
Keep MWCNTs fully dispersed in Lysozyme in Aqueous Solution, obtains uniformly mixed black mixed liquor.Then it is placed on being centrifuged
In machine under conditions of 6000 revs/min, after centrifugation 15 minutes, supernatant is taken, MWCNTs/ lysozyme composite dispersion liquid is obtained.
(4) by obtained MWCNTs/ lysozyme composite dispersion liquid and 8 parts of Nano silver solutions, 8 parts of carbon black mixing, in magnetic force
On blender, 200rmp revolving speed is stirred 3h under the conditions of 40 DEG C, then disperses complex liquid 3 minutes in cell pulverization instrument
(cell pulverization instrument power regulation is 350W)；Dispersion liquid is finally placed in drying 12 hours in 50 DEG C of thermostatic drying chamber, is obtained
To biology base composite conducting pigment.
(5) by the poly- silicon of product and the aqueous polyurethane of 25 parts by weight, the liquid paraffin of 2 parts by weight and 2 parts by weight in (4)
After ball mill mixing is poured into the mixing of the auxiliary agents such as oxygen alkane, high speed grinding is carried out to it using agate ball, revolving speed is 600 revs/min, when
Between be 1 hour, obtain uniformly mixed aqueous composite material.
(6) mixture is sieved by 200 mesh screens, takes the mixture under sieve, continued ultrasonic disperse 5 minutes, then will
Mixture is respectively coated on clean PET, silicon wafer and glass, then is placed in drying 24 hours in 60 DEG C of drying boxes, is answered
Close conductive layer.
Fig. 5 is after biology base electrically conductive ink prepared by embodiment 3 is coated on different substrate materials (PET, silicon wafer and glass) surface
Square resistance, square resistance average value is as shown in table 7.
Embodiment 4
Biology base nano conductive printing ink is prepared using the raw material of parts by weight in table 5:
5 biology base electrically conductive ink raw material proportioning table (parts by weight) of table
| Lysozyme | Multi-walled carbon nanotube | Aqueous polyurethane | Liquid paraffin | Polysiloxanes | Deionized water | Nano silver solution | Carbon black |
| 5 | 5 | 14 | 1 | 1 | 20 | 2 | 5 |
(1) the lysozyme powder that the activity of 5 parts by weight is 40000 is weighed, is dissolved, is configured to using deionized water
10-3The colorless and transparent Lysozyme in Aqueous Solution of M concentration；
(2) the untreated multi-walled carbon nanotube of 5 parts by weight (MWCNTs) is weighed, Lysozyme in Aqueous Solution is poured slowly into
In, it is placed on ultrasonic vibration 5 minutes in supersonic wave cleaning machine；
(3) mixed liquor in (2) is placed under ice bath environment, using ultrasonic cell disrupte instrument (the new sesame biotechnology in Ningbo
Limited liability company, model: JY92-IIN) ultrasound is carried out to it 1 hour, divide MWCNTs sufficiently in Lysozyme in Aqueous Solution
It dissipates, obtains uniformly mixed black mixed liquor.Then it is placed in centrifuge under conditions of 6000 revs/min, is centrifuged
After 15 minutes, supernatant is taken, obtains MWCNTs/ lysozyme composite dispersion liquid.
(4) by obtained MWCNTs/ lysozyme composite dispersion liquid and 2 parts of Nano silver solutions, 5 parts of carbon black mixing, in magnetic force
On blender, 200rmp revolving speed is stirred 3h under the conditions of 40 DEG C, then disperses complex liquid 3 minutes in cell pulverization instrument
(cell pulverization instrument power regulation is 500W)；Dispersion liquid is finally placed in drying 12 hours in 50 DEG C of thermostatic drying chamber, is obtained
To biology base composite conducting pigment.
(5) by the poly- silicon of product and the aqueous polyurethane of 14 parts by weight, the liquid paraffin of 1 parts by weight and 1 parts by weight in (4)
After ball mill mixing is poured into the mixing of the auxiliary agents such as oxygen alkane, high speed grinding is carried out to it using agate ball, revolving speed is 600 revs/min, when
Between be 1 hour, obtain uniformly mixed aqueous composite material；
(6) mixture is sieved by 200 mesh screens, takes the mixture under sieve, continued ultrasonic disperse 5 minutes, then will
Mixture is respectively coated on clean PET, silicon wafer and glass, then is placed in drying 24 hours in 60 DEG C of drying boxes, is answered
Close conductive layer.
The biology base electrically conductive ink that Fig. 6 show the preparation of embodiment 4 applies on different substrate materials (PET, silicon wafer and glass) surface
Square resistance after cloth, square resistance average value are as shown in table 7.
Embodiment 5
Biology base nano conductive printing ink is prepared using the raw material of parts by weight in table 6:
6 biology base electrically conductive ink raw material proportioning table (parts by weight) of table
| Lysozyme | Multi-walled carbon nanotube | Aqueous polyurethane | Liquid paraffin | Polysiloxanes | Deionized water | Nano silver solution | Carbon black |
| 20 | 20 | 55 | 4 | 4 | 80 | 4 | 10 |
(1) the lysozyme powder that the activity of 20 parts by weight is 40000 is weighed, is dissolved, is configured to using deionized water
10-3The colorless and transparent Lysozyme in Aqueous Solution of M concentration；
(2) the untreated multi-walled carbon nanotube of 20 parts by weight (MWCNTs) is weighed, it is water-soluble to be poured slowly into lysozyme
In liquid, it is placed on ultrasonic vibration 5 minutes in supersonic wave cleaning machine；
(3) mixed liquor in (2) is placed under ice bath environment, using ultrasonic cell disrupte instrument (the new sesame biotechnology in Ningbo
Limited liability company, model: JY92-IIN) ultrasound is carried out to it 1 hour, divide MWCNTs sufficiently in Lysozyme in Aqueous Solution
It dissipates, obtains uniformly mixed black mixed liquor.Then it is placed in centrifuge under conditions of 6000 revs/min, is centrifuged
After 15 minutes, supernatant is taken, obtains MWCNTs/ lysozyme composite dispersion liquid.
(4) by obtained MWCNTs/ lysozyme composite dispersion liquid and 4 parts of Nano silver solutions, 10 parts of carbon black mixing, in magnetic force
On blender, 200rmp revolving speed is stirred 3h under the conditions of 40 DEG C, then disperses complex liquid 3 minutes in cell pulverization instrument
(cell pulverization instrument power regulation is 400W)；Dispersion liquid is finally placed in drying 12 hours in 50 DEG C of thermostatic drying chamber, is obtained
To biology base composite conducting pigment.
(5) by the poly- silicon of product and the aqueous polyurethane of 55 parts by weight, the liquid paraffin of 4 parts by weight and 4 parts by weight in (4)
After ball mill mixing is poured into the mixing of the auxiliary agents such as oxygen alkane, high speed grinding is carried out to it using agate ball, revolving speed is 600 revs/min, when
Between be 1 hour, obtain uniformly mixed aqueous composite material；
(6) mixture is sieved by 200 mesh screens, takes the mixture under sieve, continued ultrasonic disperse 5 minutes, then will
Mixture is respectively coated on clean PET, silicon wafer and glass, then is placed in drying 24 hours in 60 DEG C of drying boxes, is answered
Close conductive layer.
The biology base electrically conductive ink that Fig. 7 show the preparation of embodiment 5 applies on different substrate materials (PET, silicon wafer and glass) surface
Square resistance after cloth, square resistance average value are as shown in table 7.
The conductive coating square resistance that each embodiment of table 7 is prepared
It can be seen from Table 7 that square resistance of the conductive coating of each embodiment preparation on silicon wafer is minimum, in flexibility
PET sheet and brittle sheet glass on square resistance similar mean values, this is because silicon wafer itself has certain electric conductivity,
And thereon by the coating of biology base electrically conductive ink, it is equivalent to and enhances the electric conductivity of silicon wafer itself.Biology base prepared by embodiment 2 is led
Square resistance of the electric ink after different substrate materials surface is coated with is smaller than embodiment 1, biology base electrically conductive ink prepared by embodiment 3
Square resistance after the coating of different substrate materials surface is smaller, illustrates that the increase of Nano silver solution content can effectively enhance leading for ink
Electrically.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (18)
1. a kind of biology base electrically conductive ink, which is characterized in that the electrically conductive ink contains protein-modified carbon nanotube, nanometer
Silver, carbon black and water-base resin, and the auxiliary agent being added as needed.
2. electrically conductive ink according to claim 1, wherein the electrically conductive ink contains protein-modified carbon nanotube 5-20
Parts by weight, nano silver, carbon black and water-base resin 14-55 parts by weight, and the auxiliary agent being added as needed；Preferably, described
Electrically conductive ink contains protein-modified carbon nanotube 5-20 parts, 0.0002-0.001 parts of nano silver, carbon black 5-10 in parts by weight
Part, 14-55 parts of water-base resin, and be added as needed 2-8 parts of auxiliary agent；Preferably, the electrically conductive ink is with parts by weight
Meter contains water 20-80 parts；
It may further be preferable that the electrically conductive ink contains protein-modified carbon nanotube 8-12 parts, water 25-35 in parts by weight
Part, 0.0003-0.0008 parts of nano silver, 6-9 parts of carbon black, 20-30 parts of water-base resin, and the auxiliary agent 4-8 being added as needed
Part；
It may further be preferable that the electrically conductive ink contains protein-modified carbon nanotube 9-11 parts, water 28-32 in parts by weight
Part, 0.0005-0.0008 parts of nano silver, 6-9 parts of carbon black, 22-27 parts of water-base resin, and the auxiliary agent 5-8 being added as needed
Part.
3. electrically conductive ink according to claim 1 or 2, wherein the protein is selected from zymoprotein, preferably lysozyme.
4. electrically conductive ink according to claim 3, wherein the activity of the lysozyme is 30000-70000；Preferably
40000-60000。
5. electrically conductive ink according to claim 1-4, wherein the carbon nanotube is selected from single-walled carbon nanotube
And/or multi-walled carbon nanotube；Preferably, the carbon nanotube diameter is 1-100nm, preferably 20-50nm.
6. electrically conductive ink according to claim 1-5, wherein the particle size range of the nano silver is 2-90nm,
It is preferred that 12-15nm.
7. electrically conductive ink according to claim 1-6, wherein the carbon black purity is higher than 90%.
8. electrically conductive ink according to claim 1-7, wherein the water-base resin is selected from aqueous polyurethane, water
Property epoxy resin, water-based acrylic resin.
9. electrically conductive ink according to claim 1-8, wherein the auxiliary agent is selected from levelling agent and/or defoaming agent,
Preferably, the levelling agent is selected from paraffin, acrylic acid levelling agent, ethylene oxide, propylene oxide and/or organosiloxane class stream
Flat agent, preferably paraffin；The defoaming agent is selected from polysiloxanes, polyethers defoaming agent, preferably polysiloxanes；Further preferred
It is that the electrically conductive ink contains 1-4 parts of levelling agents, 1-4 parts of defoaming agents in parts by weight.
10. -9 described in any item electrically conductive inks according to claim 1, wherein the protein-modified carbon nanotube pass through by
Protein separates supernatant and is made after mixing with carbon nanotube.
11. electrically conductive ink according to claim 10, wherein the protein and the mass ratio of carbon nanotube are 1:0.8-
3, preferably 1:1.
12. the preparation method of the described in any item electrically conductive inks of claim 1-11, comprising the following steps:
Step (1): protein-modified carbon nanotube, Nano silver solution and carbon black are mixed to get composite conducting pigment；
Step (2): the composite conducting pigment is mixed with water-base resin and the auxiliary agent being added as needed, is obtained aqueous compound
Material；With
Step (3) sieves the aqueous composite material by sieve, and the mixture under sieve is taken to obtain electrically conductive ink；Preferably
It is that the sieve is 100-200 mesh.
13. preparation method according to claim 12, wherein by weight, protein-modified carbon nanotube be 5-20 parts,
Nano silver solution is 2-8 parts, carbon black is 5-10 parts, water-base resin is 14-55 parts.
14. preparation method according to claim 12 or 13, wherein in step (1), the mixing includes dispersion step,
Preferably, the dispersion passes through ultrasonic disperse, it is further preferred that, the ultrasonic disperse power is 200-500W, preferably
For 260-400W；It may further be preferable that the dispersion is dispersed by cell pulverization instrument.
15. electrically conductive ink made from claim any one of 12-14.
16. a kind of composite conductive layers comprising electrically conductive ink and base described in any one of claim 1-11 or claim 15
Material.
17. composite conductive layers according to claim 16, the substrate is selected from resin, silicon wafer and/or glass.
18. the described in any item electrically conductive inks of claim 1-11 in the application of print field, are preferably led in printed electronic material
The application in domain, further preferably answering in sensor, radio electronic label, circuit board, 3D printing, display screen and field of batteries
With.
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| CN110157247A (en) * | 2019-06-24 | 2019-08-23 | 吴金花 | A kind of conductive nano ink and preparation method thereof |
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